Compositions of matter comprising mixtures of a synthetic resin containing gel and a rubber



' @aiented Dec. 6,, i949 ,noszs COMPOSITIONS OF .MATTER COMPRISING MIXTURES OF A SYNTHETIC RESIN CON- TAINING GEL AND A RUBBER Mortimer T. Harvey, South Orange, N. J assignor to- Harvei Research Corporation, a corporation of New Jersey -No Drawing. Original application April 26, 1944,

Serial No. 532,884.

Divided and this applicatime Home 7, 1946, Serial No. 675,306

Claims. 1

This invention relates to novel products and to methods for preparing the same. In one of its specific aspects this invention is directed to novel products capable of producing gels with certain compounds and to the methods for producing said products. In another aspect this invention relates to gels and millable and cured compositions and to the methods for producing said gels and millable and cured compositions. This application is a continuation in part of my copending application Serial No. 405,07d filed August 1, 1941 and now abandoned and is a division of my copending application 532,884 filed April 26, 1944, now U. S. Patent No. 2,415,096.

I have produced gels which comprised a nor-=- mally solid vinyl resin and a normally liquid unsaturated organic material. Some of said resins employed were the polymers of vinyl chloride, vinyl acetate, vinyl chloracetate and vinyl acetals such as vinyl butyral, etc., and the copolymers of vinyl chloride and vinyl acetate.

Some of the normally liquid unsaturated organic materials employed were the liquid condensation reaction products of a terpene, examples of which are turpentine, pinene, dipentine, limonine, cedar wood 01!, cedrene etc., with formaldehyde I in the presence of an acidic condensing agent greater viscosity and greater percentage of combined oxygen content when compared with the corresponding characteristics of said unsaturated organic substances in their unoxidized condition.

Said substances of said class may be oxidized to increase the ,percentage of combined oxygen therein and to increase their .vis'cosities by subjecting the same to an oxidizing agent capable of so modifying saidsubstanc'es. Among some .of the agents which may be used for this purpose are oxygen, air, ozone, and the like.

The application discloses the treatment of that class of normally liquid unsaturated organic products which when in the ratio of 5 parts of any one of said products to one part of normally solid polyvinyl chloride can be heated to an elevated temperature of about 250 F. to 350 F.

. 2 V to form a solution which upon cooling is a gel at F. The application also discloses the re sultant products produced by following the methods of this invention, which resultant products when in the-ratio of five parts of any one of said products to one part of normally solid polyvinyl chloride can be heated to an elevated temperature of about 250 F. to 350 F. to form a solution which upon cooling is a gel at 70 F.

- This invention is particularly directed to gels produced with (a) solid resinous polymers and copolymers which may be the polymers of vinyl chloride, vinyl acetate, vinyl chlcracetate, the vinyl acetals, such as vinyl butyral, etc., and copolymers of vinyl chloride and vinyl acetate and (b) 'a blown unsaturated organic condensation reaction product ,of a terpene or a terpene alcohoh with formaldehyde in the presence of an stances of said class is to blow the same withoxygen, ozone or air. Briefly stated, the novel method comprises heating above about F. a mass of said normallyliquid. unsaturated organic product capableat elevated temperatures of forming a solution with solid polyvinyl .chloride which solution on cooling is a gel at 70 F. and while said mass is in said heated condition agitating said mass in the presence'of a gas containing free oxygen until the viscosity of said mass at 25. C. has increased at least 0.5%. Al-

though temperatures greatly in excess of 140 F. may be employed, I prefer to employ a temperature range of between about 140 F. to 400 F. notwithstanding that temperature in excess of 400 F. and as high as 600 F. may be employed. While a wide variety of gas containing free oxygen may-be employed, for the purposes of illustration, I disclose the use of air, oxygen or ozone, the former being the most preferable because of its availability and low cost. The agitation of saldnormally liquid unsaturated organic product may be accomplished by flowing the material, by projecting the material, or by forcing the gas itself through the material being treated.

One of the specific methods for producing these,

novel products which method is particularly a 3 plicable commercially is to blow said normally liquid unsaturated organic product at temperatures above 140 F. with a gas containing free oxygen. The blowing may be carried out by forcing said gas through the heated product being treated, by allowing the product being treated to trickle over inclined surfaces in the presence of said gas, or by forcing the product being treated through an atomizing" nozzle to break the same into small particles which are projected into a chamber containing said gas. Any one of said specific methods may be employed alone or a combination of two or more of them may be used. This invention may be practiced at atmospheric pressure or super atmospheric pressures. These specific methods are set forth merely for the purposes of illustration and show that variations of these particular methods may be used to obtain agitation and therefore a high degree of surface contact of the product being treated to said gas so that the time of treatment may be such as to make the process commercially practicable. While the time of treatment is vari: able, depending on the temperature of the product being treated and the degree of surface contact of this product and said gas per unit of time, I prefer that the product being treated be maintained above 140? F. and a contact with the free oxygen containing gas until the viscosity at C. of the resultant product be at least 50% greater than the viscosity at 25 C. of the untreated product, and that its percentage of combined oxygen be at least 0.5% greater than the percentage of combined oxygen of the untreated product. In most cases, however, I prefer that this treatment be continued until the resultant product has a viscosity which is at least 100% greater than that of the untreated product and its combined oxygen content be at least 1% greater than that of the untreated product.

A genus of said normally liquid unsaturated organic materials capable at elevated temperature of forming a solution with a solid resin selected from the group consisting of polymers of vinyl chloride, vinyl acetate, vinyl chloracetate, and the vinyl acetals such as vinyl butyral, etc., and copolymers of vinyl chloride and vinyl acetate is the liquid organic condensation reaction products produced by reacting a terpene with formaldehyde in the presence of an acidic catalyst.

A commercially practical method for producing this genus is to react a terpene and formaldehyde in aqueous solution in the presence of an amount of an acid so limited in quantity that the pH of the aqueous phase of the mix is less than that required to cause material polymerization of the terpene. In carrying out this process, between 1 to 7 molecular proportions and preferably between 3 to 7 molecularproportions of formaldehyde are used for each molecular proportion of 60 grams of p e- This m x e of f hyde solution, sulphuric acid and dipentene was the terpene. The commercially available aqueous solution of formaldehyde containing approximately 37.5-40% formaldehyde is employed. The quantity of acid is preferably verylow and for most purposes maybe between .01 to 0.1 mole per mole of terpene."

The following Examples 1-6, inclusive, illustrate the specific manner of preparing some of said reaction products of this genus and are given for the purposes of illustration.

Erample 1 About 150 pounds of a commercial water solution of formaldehyde (about 37.5% formaldehyde the mixture was two separate layers, (a) an oily The. oily or oil-like layer was separated from the.

(U. s. naval stores) and about 250 cc. of concentrated sulphuric acid were placed together and agitated, the formaldehyde solution and the sulphuric acid being brought carefully together before the turpentine was added. This mixture of turpentine, formaldehyde solution and sulphuric acid were heated to boiling and maintained in the state of boiling under a reflux condenser.

while being constantly agitated for about nine hours. At the end of this nine hour period about 2.25 pounds of dry caustic soda was added to the resulting mix and agitated therein for about an hour in order to neutralize the sulphuric acid present. The mixture was allowed to stand for about 8 hours after which it was found to have separated into two main layers, (a) an oily or oil-like layer and (b) a watery layer. The oily or oil-like layer was separated from the water layer and placed in pans in an oven at about 275 F. to vaporize and remove any remaining water and until a practically clear solution of the condensation reaction product was obtained in a solvent such as ethyl alcohol. This oily or oillike product thusflnally obtained is hereinafter designated as product A, at 27 C. has a specific gravity of 1.08 and at 25 C. has a viscosity of 6156 centipoises.

Example 2 About 40 pounds of 37.5% formaldehyde in water solution, about 57 pounds of pinene and about 120 cc. of concentrated sulphuric acid were mixed together, the formaldehyde solution and sulphuric acid having been carefully brought together before the turpentine was added. This mixture of aqueous formaldehyde solution, turpentine and sulphuric acid was heated to boiling and maintained in this state of boiling under a reflux condenser while being constantly agitated for about nine hours. At the end of this nine hour period about .2 of a pound of dry caustic soda was added thereto and agitated therethrough to neutralize the sulphuric acid. The mixture was allowed to stand for about 8 hours after which it was found to have separated into two main layers, (a) an. oily or oil-like layer and (b) a watery layer. The oily or oil-like layer was separated from the water layer and placed in pans in an oven at 275 F. to remove any remaining water and until a practically clear solution of the same may be obtained in a solvent such as ethyl alcohol. ,This oily or oil-like product thus finally obtained is hereinafter designated as product B.

Example 3 About 900 grams of aqueous solution of formaldehyde (37.5% formaldehyde in water), were mixed with about 4 cc. of concentrated sulphuric acid. Then to said mixture was added about 544 heated to boiling and maintained in this state of boiling under a reflux condenser and while being constantly agitated for about six hours. At the end of this six hour period, about 4.3 grams of dry caustic soda was added to the resulting mix and this mixture was heated to boiling for about one more hour and then allowed to cool to about room temperature whereupon or oil-like layer and (b) a watery layer.

watery layer and dehydrated as set forth in Examples 1 and 2. The resultant oily or oil-like in water), about 100 pounds of gum turpentine layer of this example is hereinafter designated hours.

s asproductcgatsa'ahssaspecincgrsvityod' 0.971 and at 25' C. has a viscosity of i9 centi- Example 4 About 875 grams an aqueous solution of iormaldehyde containing 87.5% formaldehyde and 3.5 cc. oi concentrated sulphuric acid were mixed together and 560 grams of cedar wood oil added thereto. This mixture of formaldehyde solution, sulphuric acid and cedar wood oil was heated to boiling and maintained in this state oi boiling under a reflux condenser while being continuously agitated for a period oi about t Thereafter, 3.6 grams or dry caustic soda were added thereto and admixed therewith to neutralize the sulphuric acid. The mixture was allowed, to stand after which it was separated into two main layers, (a) an oily or oil-like layer and (b) a watery layer. The oily or oil-like layer was separated from the watery layer and placed in pans in an oven at 275 R- to remove any remaining water. This oil-like product thus finally obtained is hereinafter desisnatcd as product D, and has at 25 C. a specific gravity of 0.972 andia viscosity of i313. I

Instead of employing an aqueous solution of i'ormaldehyde in the preparation of the reaction. condensation products of terpenes and formaldehyde, the reaction may be carried out with sub-" stantially anhydrous reactants, and even in this instance the quantity of mineral acid catalyst employed is less than that required to cause some of the reaction products of said genus under said conditions:

Ell-"111716 5 of paraformaldehyde, 30 ports of glacial acetic acid and 3.3 parts of concentrated sulphuric acid sweet inathisseccndsenusistoreactaterpenealcm.

hol and formaldehyde in aqueous solution in the presence of an amount oian ocid so limited in a quantity-that the pfioi the auueousphase oi the mix is less than that requirw to cause anpreciable polymerization of the tel-pens alcohol.

in carrying out this process, between 1 and 7 molecular proportions'and preferably between mV and 7 molecular proportions of formaldehyde are used for each molecular proportion of the terpcne alcohol. Commercially available aqueous soluac tion of formaldehyde containing 37.5 to 40% for maldehyde is employed. The quantity of acid is preferably very low and for most: purposes the mole ratio of the formaldehyde to the acid catalyst in said mixture may be between about 3 to .01 and l. to 0.1.-

The iollowing Examples 7-9 ciilc manner of preparing some of the reaction products of this genus and are purposes oi' illustration:

Example 7 About 812 grams of an aqueous solution of formaldehyde containing 87.5% formaldehyde and 3.1 cc. of concentrated sulphuric acid were mixed together and 375 grams of pine oil were added thereto. This mixture of pine oil, sulphuric acid andaqueous formaldehyde was heated to boiling A and maintained in this state of boiling under con- A mixture of 402 parts of turpentine, 90 parts isheatedtdbollingandmaintainedinthisstate Example 6 A mixture of 350 parts 'of'pinene, 90 parts of paraformaldehyde, 30 parts of glacial acetic acid and 3.3 parts of concentratedsulphuric acid is. heated to boiling and maintalnedin this state while being constantly agitated for about 8 hours under a reflux condenser. The resultant mass is then neutralized by admixing therewith caustic soda after which salts precipitate out and are removed therefrom. The liquid may then be distilled to drive off the water, acetic acid; as

. well as any unreacted pinene and formaldehyde.

The remaining liquid is the organic condensanated as product F and has at 25 C. a specific gravityof 1.08 and a viscosity of 570 centipoises. A second genus of one of said normally liquid unsaturatedorganicmaterials capable at elevated temperatures-oi forming a solution with a solid stant agitation and undera reflux condenser for about six hours. Then about 4.3 grams of dry caustic soda was added thereto and admixed therewith to neutralize the sulphuric acid. At room temperature, the mix separated into two main layers, (a) an oily or oil-like layer and (b) a.

water layer. The oily or oil-like layer was dehy drated by heating as in Examples 1 and-24:0 pro-' vide reaction condensation product hereinafter designated as product (3 and having at 25 c. a specific gravity of 1.065 and a-viscosity of 1649 centipoises. 1

Example 8 About 1000 grams of 37.5% formaldehyde in water solution and 4.5 cc. of concentrated sulphuric acid were mixed together and 618 grams of oil 02 eucalyptus (product of Guatemala) were added to said mixture. This mixture of formaldehyde solution, sulphuric acid, and oil of eucalyptus was heated to boiling and maintained in' this state of boiling under a reflux condenser'while being constantly agitated for about 9 hours. Then about 4.8 grams of dry caustic sodawere added thereto and mixed therewith in order to neutralize the sulphuric acid." The mix was allowed to tion reaction product, will hereinafter be desisstand and separated into two main layers, (a) an oily or oillike layer and (b) an aqueous layer. The oil-like layer was separated from the watery layer and heated as in Examples 1 and 2 to remove any water therefrom. This condensation reaction product is hereinafter designated I. asproduct H and has at 25 C. aspeciflcgravlty of 1.005 and a viscosityof centipoises.

Instead of. employing an aqueous solution of.-

formaldehyde in the preparation ofthe reaction condensation products or ternenel. alcohols and illustrate the spe- Elven for the sneaese formaldehyde, the reaction may be carried out with substantially anhydrous reactants. and even in this instance the quantity of mineral catalyst employed'is less than that required to cause appreciable polymerization of the terpene alcohols.

The following example illustrates the manner.

of preparing some of the reaction products of this genus under said conditions:

Example 9 paraformaldehyde, 30 parts of glacial acetic acid and 3.3 parts of concentrated sulphuric acid is heated to-boiling while being constantly agitated for about eight hours under a reflux condenser.

The resultant mass is neutralized with caustic soda after which precipitated salts are removed therefrom. The liquid may be distilled to remove water, acetic acid as well as any unreacted formaldehyde and turpentine. The remaining liquid is the organic condensation reaction prodnet-hereinafter designated as product I and having ail-25 C. a specific gravity of 1.09 and a viscosity of 356 centipoises. w Throughout this description and claims, the term "formaldehyde" is employed to include formaldehyde as well as paraformaldehyde which is formaldehyde in the polymerized state.

Each of the unsaturated organic substances, of which products A-I, inclusive, are examples, capable of dissolving the aforementioned solid polyusers and copolymers and capable of forming a gel therewith, are oxidized by treating the same with air, oxygen, ozone or the like to provide a.

employed for this purpose is to blow said substances with air, oxygen, ozone or the like The blowing may be accomplished by forcing said air,

oxygen, ozone or the like through a quantity of said substance in a tank, or by spraying or fiow- A mixture of 150 parts of pine bu, 90 parts of.

ing said substances into or through an ambient of ozone, air or oxygen. In carrying out this operation, it is preferable that the substance being blown be maintained between about 160 F.-

to about 200 F. and the temperature of the air,

' oxygen or ozone be at least as high as room temperature although it may also be at the elevated temperature employed.

The following is an illustrative general example for increasing the viscosity and combined oxygen content of said unsaturated organic liquids ca- 'pable'of dissolving said vinyl resins and forming a gel therewith. I e

' q Example 10' 4 A quantity of one of said unsaturated organic liquids, such as any one of the specific products is placed into a closed container having a conduit extending through the top thereof andterminating' at a point spaced from but near the bottom thereof. The lower end of said conduit.

has a plurality of lateral openings therethrough, through which air, oxygen or ozone may be discharged and into said unsaturated organic liquid gmaintained at a temperature between about 100 F. and 300 F., while the air, oxygen or ozone,

admitted to said container may be at room temperature. The quantity of liquid in the container may be about one-quarter of the capacity thereof in order to accommodate the great deal of splashing due to the bubbling of the air, oxygen or ozone therethrough and the agitation due to stirring. .Ai'ter a period of between about 24 to 144 hours, depending upon the rate of stirring, the

rate of air, oxygen or ozone admission and the quantity of said liquid, said liquid will be found to have increased in specific gravity, viscosity and combined oxygen content when compared with the respective corresponding characteristics before said operation was begun. The combined oxygen content will have increased'at least 1% and in some cases will have increased as high as about 19% or more. The viscodty at 25 C. willhave increased at least 100% and in some cases will have increased to such a degree that it has been converted to a mass a 25 C.

Example 11 After products A, D, G and H were heated to Specific Viscosity in Products Gravity Oeutipoises at C. at 25 0.

1x650 semisolid 4458 I00 Example 12 After product C was heated to a temperature of about C. and air blown for a period of 72- hours while being maintained at said elevatedtemperature, the resulting product hereinafter designated as CO had at 25 C. a specific gravity: of 0.988 and at 25 C. a viscosity of 60 centipoises.

Example 13 I After products E, F and I are heated to an elevated temperature of about 90 C. and air blown for a period of about 6 hours while being maintained at said elevated temperature, the. resulting respective products, hereinafter designated as E0, F0 and 10 will all have been converted to a semi-solid state and all will have in creased in combined oxygen content by more than 1%. Product E0 will be found to have had a high percentage increase in combined oxygen content which is 'over 19%.

Besides these characteristics of greater combined oxygen content, higher specific gravity and viscosity, these oxidized products, of 'which products A0, C0, D0, E0, F0, GO, HO and I0 are examples, have enhanced solubility characteristics for said vinyl resins and are more readily dissolved by solid rubbery polymers of chloro-" prene, butadiene, solid rubbery copolymers of butadiene and styrene and of butadiene and acrylonitrile and by and reclaimed rubber, with all of which they act enhanced as plasticizers. These oxidized products, in addition, are

useful in the art generally and are useful parto ticularly, for example, (1) for putting vegetable which is semi-solid spray.

Improved gels are obtained by employing (a) the polymers of vinyl chloride, vinyl acetate, vinyl chloracetate and vinyl acetals, such as vinyl butyral, etc. as well as the copolymers of vinyl chloride and vinyl acetate, especially those polymers and copolymers having a molecular weight of above about 20,000 and in those cases where those having a molecular weight of about M1000 are available and (b) said oxidized unsaturated organic normally liquid products. Of this class (12), I prefer to employ those in which the terpene and terpene alcohols were the starting materials and more especially those in which turpentine and pine oil were the starting materials.

In preparing the gels with any one of said normally liquid unsaturated organic materials ,which was then oxidized to increase its viscosity and combined oxygen content, a mixture of said oxidized product and one of said normally solid vinyl resins is heated to elevated temperature and maintained at said temperature until substantially complete solution takes place. Then the solution is allowed to cool to room temperature, 70 F. at which temperature it is a gel. The

ratio of the quantity by weight of said vinyl resin to said oxidized product in said mix may vary over wide limits depending upon the type of gel desired. Generally the stifiness or the rigidity of the gel may be controlled by varying this ratio, and the stifiness and rigidity characteristic is directly proportional to this ratio, i. e., the higher this ratio, the stiller and more rigid the gel. Thus very rigid and stiff solid compositions of matter as well as soft and pliant solid compositions of matter may be produced; solid rubber-like resilient gels may be produced in this manner by employing betweenabout one totwenty-five parts of one of said oxidized prod-.

ucts to each part of said vinyl resin. In some cases, and particularly in those cases where the oxidized product is still a liquid, the same may be subjected to distillation in order to drive off some or all-those fractions having boiling points belowa predetermined temperature before the oxidized product is mixed with the vinyl resin 'so that after solution, the resultantgel at room temperature has particular characteristics ofdryness, t'ackiness or wetness desired. For example product CO was heated to remove 20% of its weight and it gave a dry gel-like product after solution with VYNW," solid copolymer of vinyl chloride and vinyl acetate when the ratio of product CO to the solid resin was to 1.

The following are specific examples of specific gels which may be produced as well as the methods which may be employed for the production of these gels, all of the parts being given by weight.

Example 14 About} parts of A0 are mixed with about 1 part of solid polyvinyl acetate, known to the trade as Vinylite AYAT." This mixture is heated to raise the, temperature of the mix to between about 290 F. and 320 F. and is maintained at this temperature and is constantly stirred or itated to provide a solution thereof. Then the solution is allowed to cool to room temperature, 70 F. and at this temperature is a gel and is a rubbery mass.

' Example 15 allowed to cool and at room temperature, 70

is a gel and a rubbery mass.

Example 16 About 3 parts of F0 are mixed with about 1 part of a, solid polyvinyl acetal, such as polyvinyl butyral, known on the market as XYFG, and prepared by treating polyvinyl alcohol with butyric aldehyde. This mixture of F0 and polyvinyl butyral is heated to a temperature of between about 290 F. to about 320 F. while being stirred to provide a solution thereof. Then the solution is allowed to cool to'room temperature, 70 F., and is a gel and a rubbery mass.

Example 17 About 25 parts of so are mixed with about 1 part of solid polyvinyl chloride. This mixture is heated to between about 290 F. and 320 F. and

maintained at this temperature while being con-: 'stantly stirred to provide a solution thereof.

Then the solution is allowed to cool to room temperature, 70 F., and at said temperature is a rubbery mass and a gel.

Novel and improved millable compositions and cured compositions are provided by employing the combination of (a) a rubbery substancesc- -lected'irom the group consisting of solid, rubbery polymers of chlorbutadiene, solid rubbery polymers of butadiene. solid rubbery copolymers of butadiene and styrene, solid rubbery copolymers of butadiene and acrylonitrile, natural rubber and reclaimed rubber and (b) a gel comprising a normally solid vinyl resin selected from the group consisting of the polymers of vinyl chloride, vinyl acetate, vinyl chloracetate and vinyl acetals, such as vinyl butyral, and copolymerso! vinyl chloride and vinyl acetate and the oxidized product of a normally liquid unsaturated organic material capable of forming a solution with said gel at elevated temperatures, which solution upon cooling is-a gel at 70 F. Other materials may be employed in said'combination, 'and some of them are carbon blacks, vulcanization agents and accelerators and an antioxidant. The relative quantity of saidnovel gel to the quantity of said rubbery substance in said combination may vary over comparatively wide limits, and is preferably such that the ratio of the quantity of said rubbery substance by weight to the quantity by weight of the resin in said gel is between about 50 to 1 and 2 to 1. Millable compositions having improved tear resistance properties may be produced by mixing a quantity of (a) together with a quantity of (b) on a rubber mill. The follow.

- lag general example is illustrative V of the invention. I

of this phase Example 18 A quantity of a rubbery substance or the aforesaid (a) class was gradually added to a quantity of a gel oi. the aforesaid (b) class while the latter was being masticated on a diil'erential speed roll mill, the mils or which were maintained at a temperature approximately about 120 1''. Milling is continued until there is an intimate admixture of these substances. Then this intimate mixture may be stripped 05 the rolls as sheets and cured. If desired, a quantity of a vulcanizing agent, accelerator and reinforcing materials as well as other material used in the compounding of rubber may be added to said mixture and dispersed therethrough on said rubber mill. This product is then sheeted and cured in the usual manner.

Since certain changes in carrying out the above I process and certain modifications in the compositions which embody the invention may be made without departing from its scope, it is intended that allmatter contained in the above description shall be interpreted as illustrative and not in a limitingsense.

8. A composition oi matter comprising (a) a substance selected irom the group consisting of rubber, reclaimed. rubber, rubbery polymers of chloroprene, rubbery polymers of butadiene, rubbery copolymers of butadiene and acrylonitrile, rubbery copolymers of butadiene and styrene, and (b) a gel comprising a normally solid resin selected from the group consisting of polyvinyl chloride, polyvinyl acetate, polyvinyl chloracetate,-

densation reaction product being capable, at elevated temperatures of forming a solution with one of said resins which solution on cooling is a 29 gel at 70 F.

Having thus described my invention, what I claim and desire to protect by Letters Patent is:

1. A composition of matter comprising (a) a substance selected from the group consisting of rubbenreclaimed rubber, rubbery polymers of ohloroprene, rubbery polymers of butadiene, rubbery-copolymers of butadiene and acrylonitrile,

rubbery copolymers of butadiene and styrene,

and (b) a gel comprising a normally solid resin selected from the group consisting of polyvinyl lsaid organic condensation reaction product being capable at elevated temperatures of forming a solution with one of said resins which solution on cooling is a gel at 70 F. v

2. A composition of matter comprising (a) a substance selected from the group consisting of rubber, reclaimed rubber, rubbery polymers of chloroprene, rubbery polymers oibutadiene, rubbery copolymers of butadiene and acrylonitrile,

rubbery copolymers of butadiene and styrene,

and (b) a gel comprising a normally solid resin selected from the group consisting of polyvinyl chloride, polyvinyl acetate, polyvinyl chloracetate, polyvinyl .butyral and copolymers of vinyl chloride and vinyl acetate, and a blown product of a normally liquid organic condensation reaction product of formaldehyde and a terpene in the presence of an acidic condensing agent, the ratio by weight of said resin to said blown product being in the range of 1-1 to 1-25 said organic condensation reaction product being capable at elevated temperatures of forming a solution with one of said resins which solutlonon cooling is a gel at 70 F.

. 4. A composition of matter comprising (a) a substance selected from the group consisting of rubber, reclaimed rubber, rubberypolymers of chloroprene, rubbery polymers of butadiene, rubbery copolymers of butadiene and acrylonitrile, rubbery copolymers of butadiene and styrene, and (b) a gel comprising a normally solid resin selected from the group consisting of polyvinyl elevated temperatures of forming a. solution with rubber, reclaimed rubber rubbery polymers of chloroprene, rubbery polymers of butadiene, rub

rubbery copolymers ofbutadiene and styrene, and (b) a gel comprising a normally solid resin selected from the group consisting of polyvim'l chloride, polyvinyl acetate, polyvinyl chloracetate, polyvinyl butyral and copolymers of vinyl chloride and vinyl acetate, and a blown product of a normally liquid organic condensation reaction product of formaldehyde and pine oil in the presence of an acidic condensing agent, the ratio by weight of said resin to said blown product being in the range of 1-1 to 1-25 said organic condensation reaction product being capable at elevated temperatures of forming a solution with one, of said resins which solution on cooling is a gel at F.

. MORTIMER T. HARVEY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

